Acetic Acid → 2-([2-Nitro-6-(trifluoromethyl)phenyl]amino}ethanol

HRID 1991199Notes

Reaction equation

HRID 1991199 reaction equation
B1([O-])OO1.[OH2:5].[OH2:6].O.O.[Na+].[NH2:10][C:11]1[C:12]([N+:21]([O-])=O)=[C:13]([C:17]([F:20])([F:19])[F:18])[CH:14]=[CH:15][CH:16]=1.[C:24]([OH:27])(=O)[CH3:25]>C(O)C>[N+:10]([C:11]1[CH:16]=[CH:15][CH:14]=[C:13]([C:17]([F:20])([F:19])[F:18])[C:12]=1[NH:21][CH2:25][CH2:24][OH:27])([O-:6])=[O:5]

Participants

5

Reactant 3

HCID 176Acetic Acid2×HCID 2230862-Nitro-3-(trifluoromethyl)anilineHCID 23693097Sodium;3-oxidodioxaborirane;tetrahydrate

Product 1

HCID 113571292-([2-Nitro-6-(trifluoromethyl)phenyl]amino}ethanolYield 29%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent2×

Conditions

Temperature
55 °C

Procedure

To a suspension of sodium perborate tetrahydrate (7.69 g, 50 mmol) in acetic acid (30 mL) a solution of 3-amino-2-nitrobenzotrifluoride (2.06 g, 10 mmol) in acetic acid (25 mL) was added dropwise at 55° C. over 1.5 h. The mixture was stirred at 55° C. overnight. Precipitated material was filtered off, and the filtrate was concentrated in vacuo. The residue was suspended in 2 M hydrochloric acid and filtered. The precipitate was washed with 2 M hydrochloric acid and water, and then dried in vacuum at room temperature affording a yellow solid, 1.14 g. This material was suspended in ethanol (10 mL), and a solution of ethanolarine (1.10 g, 18.1 mmol) in ethanol (10 mL) was added. The reaction mixture was heated at reflux for 20 min, and then allowed to cool to room temperature. The volatiles were removed in vacuo. The residue was purified by column chromatography on silica using heptane/ethyl acetate, 80:20 as an eluent affording 0.72 g (29% yield) of 2-{[2-nitro-6-(trifluoromethyl)phenyl]amino}ethanol as an orange oil. MS (ESI) m/z 249 (M−H]. 1H NMR (400 MHz, CDCl3) δ ppm 3.38-3.34 (m, 2H), 3.85-3.82 (m, 2H), 6.88-6.84 (m, 2H), 7.77 (dd, J=7.8, 1.3 Hz, 1H), 8.11 (dd, J=8.3, 1.5 Hz, 1H).

Workup

  1. additionwas added dropwise at 55° C. over 1.5 h
  2. filtrationPrecipitated material was filtered off
  3. concentrationthe filtrate was concentrated in vacuo
  4. filtrationfiltered
  5. washThe precipitate was washed with 2 M hydrochloric acid and water
  6. customdried in vacuum at room temperature
  7. customaffording a yellow solid, 1.14 g
  8. temperatureThe reaction mixture was heated
  9. temperatureat reflux for 20 min
  10. temperatureto cool to room temperature
  11. customThe volatiles were removed in vacuo
  12. customThe residue was purified by column chromatography on silica

Sources & evidence

ORD record
ord-2d5da97d36224df7a46fbe3812d66e07
Source dataset
uspto-grants-2010_01
Patent number
US07645784B2

Reaction notes

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